US20070074733A1 - Cigarettes having hollow fibers - Google Patents
Cigarettes having hollow fibers Download PDFInfo
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- US20070074733A1 US20070074733A1 US11/241,978 US24197805A US2007074733A1 US 20070074733 A1 US20070074733 A1 US 20070074733A1 US 24197805 A US24197805 A US 24197805A US 2007074733 A1 US2007074733 A1 US 2007074733A1
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- Prior art keywords
- hollow fibers
- cigarette
- filter
- smoke
- fibers
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Classifications
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- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/04—Tobacco smoke filters characterised by their shape or structure
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/02—Manufacture of tobacco smoke filters
- A24D3/0275—Manufacture of tobacco smoke filters for filters with special features
- A24D3/0291—Manufacture of tobacco smoke filters for filters with special features for hollow tipped filters, e.g. recess filters
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/04—Tobacco smoke filters characterised by their shape or structure
- A24D3/048—Tobacco smoke filters characterised by their shape or structure containing additives
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
- A24D3/062—Use of materials for tobacco smoke filters characterised by structural features
- A24D3/063—Use of materials for tobacco smoke filters characterised by structural features of the fibers
- A24D3/065—Use of materials for tobacco smoke filters characterised by structural features of the fibers with sheath/core of bi-component type structure
-
- A—HUMAN NECESSITIES
- A24—TOBACCO; CIGARS; CIGARETTES; SIMULATED SMOKING DEVICES; SMOKERS' REQUISITES
- A24D—CIGARS; CIGARETTES; TOBACCO SMOKE FILTERS; MOUTHPIECES FOR CIGARS OR CIGARETTES; MANUFACTURE OF TOBACCO SMOKE FILTERS OR MOUTHPIECES
- A24D3/00—Tobacco smoke filters, e.g. filter-tips, filtering inserts; Filters specially adapted for simulated smoking devices; Mouthpieces for cigars or cigarettes
- A24D3/06—Use of materials for tobacco smoke filters
- A24D3/14—Use of materials for tobacco smoke filters of organic materials as additive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/024—Hollow fibre modules with a single potted end
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/14—Specific spacers
Definitions
- filter materials include cotton, paper, cellulose, and certain synthetic fibers. These filter materials are known to remove particulates and condensable components from tobacco smoke. They have little or no effect in removing certain gaseous components, e.g., aldehydes, from tobacco smoke. See for example commonly assigned U.S. Pat. No. 6,209,547, which is hereby incorporated herein in its entirety for all purposes.
- Smoking articles such as cigarettes and cigarette filters, and methods of manufacturing smoking articles are provided.
- a smoking article contains hollow fibers which affect mainstream tobacco smoke drawn through the smoking article.
- a cigarette comprising: a tobacco rod; a filter joined to the tobacco rod, wherein the filter comprises a bundle of hollow fibers, wherein the lumens of the hollow fibers are aligned axially in parallel to one another; and an additive material in extra-cellular spaces of the hollow fibers, wherein one end of at least one of the hollow fibers is obstructed is provided.
- a cigarette filter comprising: hollow fibers; an outer layer covering an outer region of the hollow fibers; and cellulose acetate, wherein the hollow fibers and the outer layer are embedded within the cellulose acetate is provided.
- a method of manufacturing a cigarette filter comprising: preparing hollow fibers with a smoke impermeable material covering one end of at least one of the hollow fibers; at least partially filling extra-cellular spaces within the hollow fibers with an additive material; and placing the hollow fibers with the smoke impermeable material and the additive material in a cigarette filter is provided.
- mainstream smoke comprising: drawing tobacco smoke axially through hollow fibers, wherein the mainstream tobacco smoke is drawn into an open upstream end into lumens of the hollow fibers and is drawn through permeable walls of the hollow fibers to a downstream end of a smoking article.
- a cigarette filter comprising: a hollow fiber membrane, wherein the hollow fiber membrane comprises: hollow fibers; and a smoke impermeable material, wherein the smoke impermeable material obstructs a downstream end of a lumen of the hollow fiber.
- FIG. 1 illustrates an exemplary embodiment cigarette including a hollow fiber membrane containing filter, and a path of fluid flow through the cigarette.
- FIG. 2 illustrates a cross-section of a bundle of aligned hollow fibers with open upstream ends and impermeable or semi-permeable material filling gaps between the hollow fibers.
- FIG. 3 illustrates a cross-section of a bundle of aligned hollow fibers with closed downstream ends and permeable material filling gaps between the hollow fibers.
- FIG. 4 illustrates another exemplary embodiment cigarette including a hollow fiber membrane containing filter, and a path of fluid flow through the cigarette.
- FIG. 5 is an exemplary illustration of a cross-section of a hollow fiber.
- FIG. 6 is photomicrograph of extra-cellular spaces of an exemplary hollow fiber.
- FIG. 7 illustrates an exemplary embodiment cigarette including a hollow fiber membrane and a sorbent in a filter, and a path of fluid flow through the cigarette.
- Smoking articles include hollow fibers therein, wherein the hollow fibers are obstructed on one end to force a fluid through the walls of the hollow fibers.
- the term “feed” is used to indicate a material or fluid which is fed into the hollow fibers.
- the term “retentate” is used to indicate the portion of the feed which does not pass through the walls of the hollow fibers and is trapped within or on an outer surface of the lumens of the hollow fibers.
- filtrate is used to indicate the portion of the feed which passes through the walls of the hollow fibers.
- obstruct is intended to include blocking, partial blocking, filtering, or any other means of reducing flow through an area.
- an impermeable or semi-permeable material can be used to obstruct the downstream end of the hollow fibers by blocking filtrate or feed from passing through a downstream end of the hollow fibers, or by merely increasing the resistance to flow for filtrate or feed passing through the downstream end of the hollow fibers.
- FIG. 1 An exemplary use of a cigarette 100 with hollow fibers is illustrated in FIG. 1 , wherein the hollow fibers are utilized as hollow fiber membranes.
- a smoke feed 140 (a flow of mainstream tobacco smoke) would travel in a downstream direction.
- the smoke feed 140 would pass from the upstream end 110 through a tobacco rod 50 , then through a filter section 130 , then through the downstream end 120 of the cigarette 100 .
- the smoke feed 140 Upon entry into the filter section 130 , the smoke feed 140 is forced into lumens, or inner diameters, 15 of hollow fibers 10 within the filter section 130 .
- the lumens 15 are unobstructed on the upstream ends 25 of the hollow fibers 10 , but obstructed on the downstream ends 35 .
- the smoke feed 140 passing into the filter is directed into the upstream ends 25 of the lumens 10 by a first filtrate obstructing or smoke impermeable material 20 (hereinafter “smoke impermeable material” generally), which obstructs smoke feed 140 flow between the outer circumference of the bundle of fibers 10 and the inner diameter of the cigarette, as illustrated in FIG. 1 .
- first smoke impermeable material 20 can also be provided between the individual fibers 10 in the bundle, as illustrated in FIG. 2 , to obstruct fluid flow between the fibers 10 in the bundle.
- FIG. 3 is an exemplary cross-section illustration of the second smoke impermeable material obstructing the downstream ends 35 of the lumens 15 of the hollow fibers 10 .
- the downstream ends 35 of the hollow fibers 10 can include a filtrate permeable material 30 between the hollow fibers 10 , as well as between the outer circumference of the bundle of fibers 10 and the inner diameter of the cigarette filter 130 , if desired.
- the filtrate permeable material 30 can be any material that allows filtrate to pass through the filtrate permeable material 30 for ejection out of the downstream end 120 of the cigarette 100 .
- the filtrate permeable material 30 can be provided to hold the hollow fibers 10 in place in relation to one another, as well as in relation to the filter 130 .
- a ring, an adhesive, or other physically containing material can be used, as long as it does not substantially obstruct filtrate flow through the filter 130 .
- An exemplary embodiment of the filtrate permeable material 30 is a porous, filtrate permeable material, such as cellulose acetate.
- the walls of the hollow fibers 10 can be used to filter smoke 140 therethrough.
- the walls of the hollow fibers 10 behave as a membrane in that the walls of the hollow fibers 10 allow the filtrate 150 from the smoke 140 to pass, while the retentate (not shown) is trapped within the lumens 15 .
- the filter 130 can be reversed.
- the first smoke impermeable material 20 can be formed to obstruct an upstream end 25 of the lumens 15 so as to not allow smoke to enter the lumens 15 on the upstream end 25 of the hollow fibers 10 .
- the first smoke impermeable material 20 in FIG. 4 is formed in a similar fashion to the second smoke impermeable material 35 illustrated in FIG. 3 , wherein the first impermeable material is formed within the lumens 15 of the upstream end 25 of the hollow fibers.
- a filtrate permeable material 30 can also be provided between hollow fibers 10 for the same reasons as discussed above with respect to FIG. 3 .
- a second smoke impermeable material 30 can be used to obstruct fluid flow between the outer circumference of the bundle of hollow fibers 10 and the inner diameter of the cigarette filter 130 , as well as between the hollow fibers 10 , similar to the first smoke impermeable material 20 of the embodiment illustrated in FIG. 1 .
- smoke feed 140 can be routed between an outer circumference of the bundle of fibers 10 and the inner diameter of the cigarette filter 130 at an upstream end 25 , through the walls of the hollow fibers 10 and out the downstream end 35 .
- smoke filtrate 150 By passing the smoke filtrate 150 through the walls of the hollow fibers 10 , the hollow fibers 10 behave as a hollow fiber membrane in that the smoke is separated into retentate and filtrate 150 , wherein the retentate (not shown) can be trapped on the outer surfaces of the hollow fibers 10 .
- the filtrate 150 can then be passed through the downstream end 35 of the hollow fibers 10 .
- the hollow fibers 10 used herein are preferably embodied, as illustrated in FIG. 5 , by porous or semi-porous fibers 10 with lumens 15 (hollow inner diameters) with a wall 18 thickness with at least some porosity 19 .
- the hollow fibers can be made of any porous or semi-porous material, wherein the porosity levels can be tailored to provide predetermined levels of permeability and also to contain extra-cellular spaces therein.
- hollow fibers can be made of polymers, wherein cellulose, modified cellulose, cellulose acetate, polypropylene, polysulfone, acrylic compounds and silicone rubber are preferable embodiments. Further discussion of hollow fiber materials can be found in U.S. Pat. No. 3,708,071, which is hereby incorporated herein in its entirety by reference for all purposes.
- the material used for the hollow fibers 10 can be chosen to have a predetermined pore size by determining the materials used for the walls. For example, if the hollow fibers 10 are made of larger pore materials, larger constituent filtrates are allowed to pass through. Thus, the material used for the hollow fibers 10 can be chosen to selectively restrain passage to only certain ranges of filtrates, if desired.
- hollow fibers 10 are oriented in a direction in which smoke will travel through the smoking article. By providing such alignment, smoke can travel through lumens of the hollow fibers in a direction approximately parallel to the suction or vacuum force applied at the downstream end of the smoking article drawing smoke from the upstream or lit end.
- the hollow fibers 10 are approximately parallel to the one another in order to allow smoke feed 140 to evenly penetrate the hollow fibers 10 , pass through the walls of the hollow fibers evenly, and for fitting bundles of hollow fibers into the axis of a cigarette.
- the axes of the lumens 15 are preferably aligned parallel to one another (as well as parallel to the axis of the cigarette), wherein such alignment allows smoke feed 140 to flow through the multiple lumens directly (i.e., without detour or indirect routing) while smoking of the cigarette.
- hollow fibers 10 can be used within any smoking article, like a traditional or non-traditional cigarette, e.g., in a cigarette filter.
- Preferred embodiments provide hollow fibers for use in smoking articles, such as cigarettes and non-traditional cigarettes.
- Non-traditional cigarettes include, by way of example, cigarettes for electrical smoking systems as described in commonly-assigned U.S. Pat. Nos. 6,026,820; 5,988,176; 5,915,387; 5,692,526; 5,692,525; 5,666,976; and 5,499,636, the disclosures of which are hereby incorporated by reference herein in their entireties.
- Hollow fibers are preferably sized to a length less than the length of a filter so that the entire length of the fiber can fit within the area of the filter as the hollow fibers are aligned in the direction of smoke flow. Also, the diameters of the lumens of the hollow fibers (in combination with the material used to make the hollow fibers and the density of any bundle of hollow fibers) control the amount of flow possible, as well as the force required to pull the tobacco smoke through the hollow fibers (hereinafter, resistance to draw (RTD)).
- RTD resistance to draw
- hollow fibers can also be used to provide additives.
- hollow fibers can include porosities (i.e., extra-cellular spaces) in the walls of the hollow fibers. Within these extra-cellular spaces, additive materials can be stored, wherein the additive materials can be by fluids, such as smoke, passing through the walls of the hollow fibers and thus through the extra-cellular spaces.
- the outer diameter and wall thickness of the hollow fibers are preferably sized to optimize the hollow fibers' ability to hold additive materials and to control filtrate flow through the walls and retentate trapping on the walls . It is noted that additive materials tend not to be absorbed in the lumen of the hollow fibers due to capillary forces, thus the holding of additive materials is primarily carried out by the extra-cellular spaces within the walls. As the outer diameter of the hollow fibers increases, and/or the number of hollow fibers provided increases, the amount of the porous spaces within walls of a hollow fiber (i.e., extra-cellular spaces, such as crack or crevices in walls of hollow fibers) would tend to increase. By increasing the amount of extra-cellular spaces, more additive materials can be absorbed. On the other hand, narrower lumens, and/or fewer hollow fibers can cause the hollow fibers to hold less additive materials due to their lesser total outer surface wall areas.
- Preferred embodiment hollow fibers 10 are used to releasably hold additive materials within the extra-cellular spaces of the hollow fibers 10 .
- additive materials in the hollow fibers 10 can be sufficiently contained to substantially avoid or minimize unwanted migration of the additive materials, such as, for example, during storage of the smoking articles with the additive materials therein.
- the additive materials are provided for absorption or adsorption within the extra-cellular spaces of the hollow fibers 10 .
- additive materials can be provided by soaking the hollow fibers 10 in a bath of additive materials, wherein the additive material can be absorbed into the extra-cellular spaces.
- the hollow fibers can have a lumen (i.e., inner) diameter of approximately 50 microns to approximately 1500 microns (e.g., 50-100, 100-150, 150-250, 350-500, 500-1000, or 1000-1500 microns), preferably approximately 90 microns to approximately 450 microns.
- the hollow fibers can have a highly porous wall with a thickness of approximately 10 microns to 100 microns, preferably approximately 10 to approximately 50 microns, and an outer diameter of approximately 100 microns to approximately 2100 microns, preferably 100 to approximately 500 microns.
- an exemplary embodiment cigarette can be designed to include a bundle of 10 to 15 hollow fibers, wherein each hollow fiber has a lumen diameter of approximately 200 microns, a wall thickness of approximately 50 microns with an outer diameter of approximately 350 microns.
- Hollow fibers can be made by spinning or other fiber making techniques.
- methods of making hollow fibers have been described in U.S. Pat. Nos. 2,999,296 and 4,234,431, which are hereby incorporated herein in their entireties by reference.
- the hollow fibers 10 are cut or otherwise made to a specific length.
- the hollow fibers 10 can preferably be used in a circumferentially spaced relation in a filter section of a smoking article or can be gathered into a bundle prior to insertion into a final product. If the hollow fibers are bundled, the hollow fibers 10 can be held together using a permeable, semi-permeable or impermeable material, as mentioned above, an enclosure, such as a ring, or an adhesive, such as triacetin, epoxy, and silicone rubber.
- the additive materials are preferably mobile enough within the extra-cellular spaces of the hollow fibers to be released therefrom upon demand.
- the additive material can preferably be released from the hollow fibers upon application of a vacuum force or drawing action as mentioned above.
- Hollow fibers 10 can also be incorporated into a cigarette filter to provide a means for controlling a resistance to draw (RTD) in a cigarette.
- a cigarette filter would include hollow fibers 10 therein. By providing hollow fibers in a cigarette, a cigarette can be provided with as little or as much resistance to draw as desired.
- hollow fibers 10 can be used to supplement or replace multi-section filter assemblies, which are often more difficult to manufacture than hollow fibers 10 .
- hollow fibers 10 in cigarette filters could be used to simplify the manufacturing process while still providing tailored levels of RTD.
- first and second filtrate obstructing or smoke impermeable materials can be used to obstruct smoke flow through a smoking article as illustrated in FIGS. 1 and 4 .
- These filtrate obstructing or smoke impermeable materials along with semi-permeable or permeable material used to hold the hollow fibers can be generally referred to as “potting material.”
- potting material is intended to include materials that can be used to hold hollow fibers in place, as well as materials that can direct feed, filtrate, and retentate flow in, around and through lumens of the hollow fibers.
- the potting material can be made of any non-toxic, permeable, semi-permeable or impermeable material that can hold the hollow fibers in a fixed positional relationship with one another (i.e., in parallel to one another). Further discussion of hollow fiber membranes in potting material can be found in U.S. Pat. Nos. 3,228,887, 3,528,553 and 6,685,832, which are hereby incorporated herein in their entireties by reference.
- the potting material is a polymer or a composite, wherein the material can be selected depending upon the degree of permeability desired.
- a filtrate impermeable or semi-permeable potting material may be desired.
- epoxy is a filtrate impermeable potting material.
- a permeable potting material may be desired.
- cellulose acetate is a permeable potting material.
- the potting material can be formed on any portion of the hollow fibers 10 .
- the potting material can be formed on a portion or the entirety of the length, the circumference of the fibers, and/or on ends of the hollow fibers.
- the potting material is preferably formed on less than the entire surface of the hollow fibers, as to allow for at least some filtrate to pass through walls 18 of the hollow fibers 10 .
- coverage by the potting material on the hollow fibers 10 is preferably less than 90% of the wall surface of the hollow fibers 10 , and even more preferably, less than 60% of the wall surface of the hollow fibers 10 (e.g., 100-90%, 90-80%, 80-70%, 70-60%, 60-50%, 50-40%, 40-30%, 30-20%, 20-10% or 10-0%).
- the potting material can be formed on the hollow fibers in any manner that provides the airflow controlling properties desired by the embodiment.
- methods of forming potting material on hollow fibers have been discussed in U.S. Pat. Nos. 6,702,561, 6,663,745, 6,623,637 and 5,480,553, which are incorporated herein in their entireties by reference.
- the potting material can be made of any material that can obstruct smoke passage.
- the potting material can be made of an impermeable, semi-permeable or permeable material. If the potting material is a semi-permeable or permeable material, then the potting material can be used as permeable barrier and can increase the resistance to airflow therethrough.
- a smoking article can be provided with hollow fibers in a conformation such that the structure and orientation for the hollow fibers 10 allows for at least some of the extra-cellular spaces of hollow fibers 10 to be accessible to hollow fibers. Additionally, as provided herein, the smoke flow can still be at least partially directed through the lumens 15 and the walls 18 of the hollow fibers 10 , wherein additive materials in the extra-cellular spaces can interact with the airflow as it passes through the walls 18 of the hollow fibers 10 .
- the hollow fibers 10 can also include an outer layer covering or encapsulating the hollow fibers 10 (with additive material therein, if desired).
- the outer layer is a solid wall or film, wherein the solid wall or film can be used to temporarily seal or encapsulate the hollow fibers 10 (and anything encapsulated within the hollow fibers 10 ) away from the surrounding environment.
- the outer layer is applied around the outer surfaces of the hollow fibers 10 such that additive materials added to the hollow fibers 10 can be sealed within the hollow fibers 10 , and/or within their extra-cellular spaces.
- the outer layer is preferably easily frangible and can be ruptured to allow additive materials to be released from the hollow fibers 10 .
- the outer layer can be any frangible material, such as a polymer, which is capable of both sealing the hollow fibers, as well as breaking, rupturing or perforating on demand.
- the outer layer is made of sugar or pectin, which can also be provided to flavor filtrate, such as smoke filtrate, contacting the outer layer if desired.
- the outer layer is preferably used to immobilize additive materials within the hollow fibers 10 , and thus preferably reduces dissipation of the additive material until the outer layer is broken, ruptured or perforated.
- the outer layer is a frangible thin film.
- a difference in fluid pressure on either side of the outer layer and the hollow fiber walls i.e., drawing on a cigarette with hollow fibers and the outer layer therein
- a difference in fluid pressure on either side of the outer layer and the hollow fiber walls i.e., drawing on a cigarette with hollow fibers and the outer layer therein
- the outer layer can break to release the additive materials therefrom.
- an outer layer in a cigarette, can be designed to break when smoke is drawn through the walls of the hollow fibers, wherein the vacuum pressure of drawing the smoke can cause the outer layer to break.
- the vacuum pressure of drawing the smoke can cause the outer layer to break.
- the outer layer can be formed by any method capable of applying a film that is sufficiently thin to allow vacuum pressure to rupture the film.
- the outer layer is applied by spraying a film forming material onto the outer surfaces of hollow fibers and allowing for the film forming material to solidify into a film to provide an outer layer.
- the hollow fibers 10 are used in smoking articles, along with sorbents, such as microporous materials, to filter or remove gas phase constituents from cigarette smoke.
- sorbents such as microporous materials
- Sorbents i.e., microporous sorbents
- an activated carbon and/or a zeolite sorbent can be used.
- sorbents can hinder a cigarette designer's ability to add materials, such as volatile flavor components like menthol, as the sorbents can adsorb and/or absorb migrating volatile compounds during the time between cigarette manufacture and its being smoked.
- hollow fibers 10 can be used to overcome this problem by containing and isolating the additive materials from the sorbent prior to smoking, and therefore avoiding interaction between the additive materials and the sorbent during storage.
- a molecular sieve material in addition to the hollow fibers 10 and the sorbent, can also be present.
- the molecular sieve material can be present in monolithic or particle form sized at about 0.1 mm to 1 mm, and more preferably 0.3 mm to about 0.9 mm (e.g., 0.3 mm to 0.4 mm, 0.4 mm to 0.5 mm, 0.5 mm to 0.6 mm, 0.7 mm to 0.8 mm or 0.8 mm to 0.9 mm) to facilitate processing into cigarette filters so as to achieve a desirable filter pressure drop or RTD (resistance to draw).
- RTD resistance to draw
- filter constructions known in the art can be used, in which hollow fibers 10 can be incorporated.
- Exemplary filter structures that can be used include, but are not limited to, a mono filter, a dual filter, a triple filter, a single or multi cavity filter, a recessed filter, a free-flow filter, combinations thereof and the like.
- Filter elements are typically constructed from cellulose acetate tow or cellulose paper materials.
- Triple filters can include mouth and smoking material or tobacco side segments, and a middle segment comprising paper.
- Cavity filters include two spaced-apart filter plugs.
- the filters can also be ventilated and/or comprise additional sorbents (such as activated carbon), catalysts or other additives suitable for use in a cigarette filter.
- a cigarette 100 with a bundle of hollow fibers 10 in the filter 130 can also include a sorbent 60 .
- a cigarette 100 can be provided with a filter 130 which includes hollow fibers 10 with an additive material, such as a flavorant, therein and a sorbent upstream 60 (away from the smoker and toward the tobacco portion 50 ).
- an additive material such as a flavorant
- sorbents are typically effective for adsorbing or absorbing material added, such as a flavorant
- placing the sorbent 60 upstream from the flavorant in the hollow fibers 10 can reduce the level of absorption or adsorption of the flavorant by the sorbent 60 .
- the hollow fibers 10 can be located in a portion of the filter 130 downstream from the sorbent 60 with a section of filter material 70 , such as cellulose acetate, between the two, as illustrated in FIG. 7 .
- the hollow fibers 10 and the sorbent 60 if provided, would be placed in cavities within a filter assembly 40 .
- both the hollow fibers 10 and the sorbent 60 can be placed anywhere within a filter 130 of a smoking article.
- the hollow fibers 10 can also be used in smoking articles without a sorbent in the filter, as illustrated in FIGS. 1 and 4 . Regardless of the type of article in which the hollow fibers 10 is incorporated, the hollow fibers 10 can be used to provide effective containment and delivery of materials, such as volatile flavors or other smoking related chemicals.
- Hollow fibers can desirably be used to encapsulate additives in a smoking article, as mentioned above, wherein additives can be encapsulated within extra-cellular spaces of the hollow fibers.
- additives can both be protected from loss and can be mixed with entrainment air as air passes through the walls of the hollow fibers.
- hollow fibers 10 are preferably soaked in additives. Soaking allows the additives to be absorbed into extra-cellular spaces 35 of hollow fibers 10 , where the additives can remain due to capillary forces, thus preventing dissipation of the additives.
- the hollow fibers 10 can preferably be placed in a smoking article, more preferably a cigarette filter, where the hollow fibers 10 are aligned in a cigarette for airflow.
- the long axes of the hollow fibers 10 can be aligned with the long axis of the cigarette for airflow purposes.
- a downstream potting material 30 can be used to obstruct fluid flow through the downstream end of the hollow fibers 10 .
- an outer layer can be formed on the hollow fibers 10 in order to prevent dissipation and to further encapsulate additive materials in extra-cellular spaces of the hollow fibers, as mentioned above.
- the additives can be flavors, which can be selected from any number of known artificial and natural materials, such as, for example, peppermint, spearmint, wintergreen, menthol, cinnamon, chocolate, coffee, tobacco, vanillin, licorice, clove, anise, sandalwood, geranium, rose oil, vanilla, lemon oil, cassia, spearmint, fennel, ginger, ethylacetate, isoamylacetate, propylisobutyrate, isobutylbutyrate, ethylbutyrate, ethylvalerate, benzylformate, limonene, cymene, pinene, linalool, geraniol, citronellol, citral, peppermint oil, orange oil, coriander oil, borneol, fruit extract and the like.
- artificial and natural materials such as, for example, peppermint, spearmint, wintergreen, menthol, cinnamon, chocolate, coffee, tobacco, vanillin,
- tobacco flavorants are those described in U.S. Pat. Nos. 3,580,259; 3,625,224; 3,722,516; 3,750,674; 3,879,425; 3,881,025; 3,884,247; 3,890,981; 3,903,900; 3,914,451; 3,915,175; 3,920,027; 3,924,644; 3,966,989; 4,318,417; and the like, which are incorporated herein by reference in their entirety.
- the additives can also be chemicals, wherein the chemicals can be used to attract or repel aerosols, or react with smoke constituents to remove or chemically extract smoke constituents.
- chemicals which can be used to attract or repel aerosols include surfactants containing distinct hydrophobic (apolar) and hydrophilic (polar) regions.
- polar surfactants can be used to attract or repel selected tobacco smoke constituents like polar tobacco constituents due to intrinsic attractive polarity properties.
- these tobacco smoke constituents can be trapped and held within the hollow fibers chemically (in addition to mechanically being selectively separated by pore size of the walls of the hollow fibers, as mentioned above).
- chemicals or chemical systems can also be used to react with smoke constituents to remove smoke constituents.
- chemical systems such as aminopropylsilyl (APS), aminoethyl aminopropylsilyl (AEAPS) and aminoethylaminoethyl aminopropylsilyl (AEAEAPS) can be used. See commonly assigned U.S. Pat. Nos. 6,595,218 and 6,209,547, both of which are hereby incorporated herein by reference in their entirety.
- chemicals can also be used to react with smoke constituents to extract smoke constituents.
- chemical extractive smoking is intended to mean providing predetermined tobacco smoke constituents to a smoker without any combustion of tobacco (i.e., smokeless smoking).
- Chemical extractive smoking provides a chemical or reagent, such as water or alcohol, for interaction with tobacco in a tobacco product.
- a tobacco enriched chemical or reagent can be formed, which in turn can be inhaled as a vapor or aerosol.
- the chemical or reagent can be solvents, such as water or alcohol, such as ethyl alcohol.
- the chemical extractive smoking occurs at lower than combustion temperatures; however heat can be utilized to promote vaporization (or volatilization) of the tobacco enriched chemical or reagent.
- heat can be used to increase the vapor and the solubility of the tobacco constituents for “smoking.”
- the tobacco enriched chemical or reagent can be heat vaporized and the mobilization of the tobacco properties within the vapor can potentially be increased.
- a cigarette can be made with hollow fibers including immobilized chemicals therein.
- the drawing action on one side of the hollow fibers 10 releases chemicals into the tobacco, whereupon the chemicals cause extractive release of a tobacco aerosol.
Abstract
Smoking articles, such as cigarettes and cigarette filters, methods of manufacturing smoking articles including hollow fibers, and methods of smoking are provided. In one exemplary embodiment, a smoking article contains hollow fibers, wherein the hollow fibers change properties of mainstream tobacco smoke drawn through the hollow fibers.
Description
- A wide variety of materials have been suggested in the art as filters for tobacco smoke. Such filter materials include cotton, paper, cellulose, and certain synthetic fibers. These filter materials are known to remove particulates and condensable components from tobacco smoke. They have little or no effect in removing certain gaseous components, e.g., aldehydes, from tobacco smoke. See for example commonly assigned U.S. Pat. No. 6,209,547, which is hereby incorporated herein in its entirety for all purposes.
- Smoking articles, such as cigarettes and cigarette filters, and methods of manufacturing smoking articles are provided. In one exemplary embodiment, a smoking article contains hollow fibers which affect mainstream tobacco smoke drawn through the smoking article.
- In another exemplary embodiment, a cigarette, comprising: a tobacco rod; a filter joined to the tobacco rod, wherein the filter comprises a bundle of hollow fibers, wherein the lumens of the hollow fibers are aligned axially in parallel to one another; and an additive material in extra-cellular spaces of the hollow fibers, wherein one end of at least one of the hollow fibers is obstructed is provided.
- In another exemplary embodiment, a cigarette filter, comprising: hollow fibers; an outer layer covering an outer region of the hollow fibers; and cellulose acetate, wherein the hollow fibers and the outer layer are embedded within the cellulose acetate is provided.
- In another exemplary embodiment, a method of manufacturing a cigarette filter, comprising: preparing hollow fibers with a smoke impermeable material covering one end of at least one of the hollow fibers; at least partially filling extra-cellular spaces within the hollow fibers with an additive material; and placing the hollow fibers with the smoke impermeable material and the additive material in a cigarette filter is provided.
- Also provided is a method of treating mainstream smoke, comprising: drawing tobacco smoke axially through hollow fibers, wherein the mainstream tobacco smoke is drawn into an open upstream end into lumens of the hollow fibers and is drawn through permeable walls of the hollow fibers to a downstream end of a smoking article.
- Also provided is a cigarette filter, comprising: a hollow fiber membrane, wherein the hollow fiber membrane comprises: hollow fibers; and a smoke impermeable material, wherein the smoke impermeable material obstructs a downstream end of a lumen of the hollow fiber.
-
FIG. 1 illustrates an exemplary embodiment cigarette including a hollow fiber membrane containing filter, and a path of fluid flow through the cigarette. -
FIG. 2 illustrates a cross-section of a bundle of aligned hollow fibers with open upstream ends and impermeable or semi-permeable material filling gaps between the hollow fibers. -
FIG. 3 illustrates a cross-section of a bundle of aligned hollow fibers with closed downstream ends and permeable material filling gaps between the hollow fibers. -
FIG. 4 illustrates another exemplary embodiment cigarette including a hollow fiber membrane containing filter, and a path of fluid flow through the cigarette. -
FIG. 5 is an exemplary illustration of a cross-section of a hollow fiber. -
FIG. 6 is photomicrograph of extra-cellular spaces of an exemplary hollow fiber. -
FIG. 7 illustrates an exemplary embodiment cigarette including a hollow fiber membrane and a sorbent in a filter, and a path of fluid flow through the cigarette. - Smoking articles are provided that include hollow fibers therein, wherein the hollow fibers are obstructed on one end to force a fluid through the walls of the hollow fibers.
- As used herein, the term “feed” is used to indicate a material or fluid which is fed into the hollow fibers. Also as used herein, the term “retentate” is used to indicate the portion of the feed which does not pass through the walls of the hollow fibers and is trapped within or on an outer surface of the lumens of the hollow fibers. Additionally, the term “filtrate” is used to indicate the portion of the feed which passes through the walls of the hollow fibers.
- The term “obstruct” is intended to include blocking, partial blocking, filtering, or any other means of reducing flow through an area. For example, an impermeable or semi-permeable material can be used to obstruct the downstream end of the hollow fibers by blocking filtrate or feed from passing through a downstream end of the hollow fibers, or by merely increasing the resistance to flow for filtrate or feed passing through the downstream end of the hollow fibers.
- An exemplary use of a
cigarette 100 with hollow fibers is illustrated inFIG. 1 , wherein the hollow fibers are utilized as hollow fiber membranes. As illustrated inFIG. 1 , upon lighting acigarette 100 at anupstream end 110 of thecigarette 100 and applying a drawing action to thedownstream end 120, a smoke feed 140 (a flow of mainstream tobacco smoke) would travel in a downstream direction. Thesmoke feed 140 would pass from theupstream end 110 through atobacco rod 50, then through afilter section 130, then through thedownstream end 120 of thecigarette 100. - Upon entry into the
filter section 130, thesmoke feed 140 is forced into lumens, or inner diameters, 15 ofhollow fibers 10 within thefilter section 130. InFIG. 1 , thelumens 15 are unobstructed on theupstream ends 25 of thehollow fibers 10, but obstructed on thedownstream ends 35. Thesmoke feed 140 passing into the filter is directed into theupstream ends 25 of thelumens 10 by a first filtrate obstructing or smoke impermeable material 20 (hereinafter “smoke impermeable material” generally), which obstructssmoke feed 140 flow between the outer circumference of the bundle offibers 10 and the inner diameter of the cigarette, as illustrated inFIG. 1 . - Additionally, the first smoke
impermeable material 20 can also be provided between theindividual fibers 10 in the bundle, as illustrated inFIG. 2 , to obstruct fluid flow between thefibers 10 in the bundle. An exemplary cross-section illustration of the first smokeimpermeable material 20 surrounding thehollow fibers 10 in the bundle, while not obstructing theupstream end 25 of thelumens 15, is illustrated inFIG. 2 . - Next, also as illustrated in
FIG. 1 , thesmoke feed 140 is forced from thelumens 15 through the walls of thehollow fibers 10 by a second smoke impermeable material, which obstructs thedownstream ends 35 oflumens 15 of thehollow fibers 10.FIG. 3 is an exemplary cross-section illustration of the second smoke impermeable material obstructing thedownstream ends 35 of thelumens 15 of thehollow fibers 10. - It is noted that as illustrated in
FIG. 3 , thedownstream ends 35 of thehollow fibers 10 can include a filtratepermeable material 30 between thehollow fibers 10, as well as between the outer circumference of the bundle offibers 10 and the inner diameter of thecigarette filter 130, if desired. As provided herein, the filtratepermeable material 30 can be any material that allows filtrate to pass through the filtratepermeable material 30 for ejection out of thedownstream end 120 of thecigarette 100. - The filtrate
permeable material 30 can be provided to hold thehollow fibers 10 in place in relation to one another, as well as in relation to thefilter 130. Alternatively, a ring, an adhesive, or other physically containing material can be used, as long as it does not substantially obstruct filtrate flow through thefilter 130. An exemplary embodiment of the filtratepermeable material 30 is a porous, filtrate permeable material, such as cellulose acetate. - By obstructing the
downstream ends 35 of thehollow fibers 10,smoke 140 is forced through the walls of thehollow fibers 10 because of the pressure exerted by the smoker on thedownstream end 120. By forcingsmoke 140 through thehollow fibers 10, the walls of thehollow fibers 10 can be used to filtersmoke 140 therethrough. Thus, the walls of thehollow fibers 10 behave as a membrane in that the walls of thehollow fibers 10 allow thefiltrate 150 from thesmoke 140 to pass, while the retentate (not shown) is trapped within thelumens 15. - It is noted that in another exemplary embodiment, illustrated in
FIG. 4 , which is similar toFIG. 1 , thefilter 130 can be reversed. In other words, the first smokeimpermeable material 20 can be formed to obstruct anupstream end 25 of thelumens 15 so as to not allow smoke to enter thelumens 15 on theupstream end 25 of thehollow fibers 10. It is noted that the first smokeimpermeable material 20 inFIG. 4 is formed in a similar fashion to the second smokeimpermeable material 35 illustrated inFIG. 3 , wherein the first impermeable material is formed within thelumens 15 of theupstream end 25 of the hollow fibers. Additionally, similar toFIG. 3 , a filtratepermeable material 30 can also be provided betweenhollow fibers 10 for the same reasons as discussed above with respect toFIG. 3 . - Additionally, as also illustrated in
FIG. 4 , a second smokeimpermeable material 30 can be used to obstruct fluid flow between the outer circumference of the bundle ofhollow fibers 10 and the inner diameter of thecigarette filter 130, as well as between thehollow fibers 10, similar to the first smokeimpermeable material 20 of the embodiment illustrated inFIG. 1 . - By providing the two smoke
impermeable materials smoke feed 140 can be routed between an outer circumference of the bundle offibers 10 and the inner diameter of thecigarette filter 130 at anupstream end 25, through the walls of thehollow fibers 10 and out thedownstream end 35. By passing the smoke filtrate 150 through the walls of thehollow fibers 10, thehollow fibers 10 behave as a hollow fiber membrane in that the smoke is separated into retentate and filtrate 150, wherein the retentate (not shown) can be trapped on the outer surfaces of thehollow fibers 10. After passing through the walls of thehollow fibers 10, thefiltrate 150 can then be passed through thedownstream end 35 of thehollow fibers 10. - The
hollow fibers 10 used herein are preferably embodied, as illustrated inFIG. 5 , by porous orsemi-porous fibers 10 with lumens 15 (hollow inner diameters) with awall 18 thickness with at least someporosity 19. The hollow fibers can be made of any porous or semi-porous material, wherein the porosity levels can be tailored to provide predetermined levels of permeability and also to contain extra-cellular spaces therein. For example, hollow fibers can be made of polymers, wherein cellulose, modified cellulose, cellulose acetate, polypropylene, polysulfone, acrylic compounds and silicone rubber are preferable embodiments. Further discussion of hollow fiber materials can be found in U.S. Pat. No. 3,708,071, which is hereby incorporated herein in its entirety by reference for all purposes. - It is noted that the material used for the
hollow fibers 10 can be chosen to have a predetermined pore size by determining the materials used for the walls. For example, if thehollow fibers 10 are made of larger pore materials, larger constituent filtrates are allowed to pass through. Thus, the material used for thehollow fibers 10 can be chosen to selectively restrain passage to only certain ranges of filtrates, if desired. - In a preferred smoking article,
hollow fibers 10 are oriented in a direction in which smoke will travel through the smoking article. By providing such alignment, smoke can travel through lumens of the hollow fibers in a direction approximately parallel to the suction or vacuum force applied at the downstream end of the smoking article drawing smoke from the upstream or lit end. - Additionally, the
hollow fibers 10 are approximately parallel to the one another in order to allow smoke feed 140 to evenly penetrate thehollow fibers 10, pass through the walls of the hollow fibers evenly, and for fitting bundles of hollow fibers into the axis of a cigarette. For example, as illustrated inFIG. 1 , the axes of thelumens 15 are preferably aligned parallel to one another (as well as parallel to the axis of the cigarette), wherein such alignment allowssmoke feed 140 to flow through the multiple lumens directly (i.e., without detour or indirect routing) while smoking of the cigarette. - These
hollow fibers 10 can be used within any smoking article, like a traditional or non-traditional cigarette, e.g., in a cigarette filter. Preferred embodiments provide hollow fibers for use in smoking articles, such as cigarettes and non-traditional cigarettes. Non-traditional cigarettes include, by way of example, cigarettes for electrical smoking systems as described in commonly-assigned U.S. Pat. Nos. 6,026,820; 5,988,176; 5,915,387; 5,692,526; 5,692,525; 5,666,976; and 5,499,636, the disclosures of which are hereby incorporated by reference herein in their entireties. - Hollow fibers are preferably sized to a length less than the length of a filter so that the entire length of the fiber can fit within the area of the filter as the hollow fibers are aligned in the direction of smoke flow. Also, the diameters of the lumens of the hollow fibers (in combination with the material used to make the hollow fibers and the density of any bundle of hollow fibers) control the amount of flow possible, as well as the force required to pull the tobacco smoke through the hollow fibers (hereinafter, resistance to draw (RTD)).
- In addition to using hollow fibers as hollow fiber membranes to filter materials, such as smoke, therethrough, the hollow fibers can also be used to provide additives. For example, as illustrated in
FIG. 6 , hollow fibers can include porosities (i.e., extra-cellular spaces) in the walls of the hollow fibers. Within these extra-cellular spaces, additive materials can be stored, wherein the additive materials can be by fluids, such as smoke, passing through the walls of the hollow fibers and thus through the extra-cellular spaces. - The outer diameter and wall thickness of the hollow fibers are preferably sized to optimize the hollow fibers' ability to hold additive materials and to control filtrate flow through the walls and retentate trapping on the walls . It is noted that additive materials tend not to be absorbed in the lumen of the hollow fibers due to capillary forces, thus the holding of additive materials is primarily carried out by the extra-cellular spaces within the walls. As the outer diameter of the hollow fibers increases, and/or the number of hollow fibers provided increases, the amount of the porous spaces within walls of a hollow fiber (i.e., extra-cellular spaces, such as crack or crevices in walls of hollow fibers) would tend to increase. By increasing the amount of extra-cellular spaces, more additive materials can be absorbed. On the other hand, narrower lumens, and/or fewer hollow fibers can cause the hollow fibers to hold less additive materials due to their lesser total outer surface wall areas.
- Preferred embodiment
hollow fibers 10 are used to releasably hold additive materials within the extra-cellular spaces of thehollow fibers 10. Thus, because of the releasable hold, additive materials in thehollow fibers 10 can be sufficiently contained to substantially avoid or minimize unwanted migration of the additive materials, such as, for example, during storage of the smoking articles with the additive materials therein. - In order to provide additive materials in hollow fibers, the additive materials are provided for absorption or adsorption within the extra-cellular spaces of the
hollow fibers 10. For example, additive materials can be provided by soaking thehollow fibers 10 in a bath of additive materials, wherein the additive material can be absorbed into the extra-cellular spaces. - Therefore, in an average sized cigarette (e.g., a cigarette with a length between 65-100 mm, a diameter of 6-9 mm and a filter length of 15-30 mm), the hollow fibers can have a lumen (i.e., inner) diameter of approximately 50 microns to approximately 1500 microns (e.g., 50-100, 100-150, 150-250, 350-500, 500-1000, or 1000-1500 microns), preferably approximately 90 microns to approximately 450 microns. Additionally, the hollow fibers can have a highly porous wall with a thickness of approximately 10 microns to 100 microns, preferably approximately 10 to approximately 50 microns, and an outer diameter of approximately 100 microns to approximately 2100 microns, preferably 100 to approximately 500 microns.
- For example, an exemplary embodiment cigarette can be designed to include a bundle of 10 to 15 hollow fibers, wherein each hollow fiber has a lumen diameter of approximately 200 microns, a wall thickness of approximately 50 microns with an outer diameter of approximately 350 microns.
- Hollow fibers can be made by spinning or other fiber making techniques. For example, methods of making hollow fibers have been described in U.S. Pat. Nos. 2,999,296 and 4,234,431, which are hereby incorporated herein in their entireties by reference.
- In order to use the
hollow fibers 10 in a smoking article, thehollow fibers 10 are cut or otherwise made to a specific length. Thehollow fibers 10 can preferably be used in a circumferentially spaced relation in a filter section of a smoking article or can be gathered into a bundle prior to insertion into a final product. If the hollow fibers are bundled, thehollow fibers 10 can be held together using a permeable, semi-permeable or impermeable material, as mentioned above, an enclosure, such as a ring, or an adhesive, such as triacetin, epoxy, and silicone rubber. - Additionally, because of the releasable hold, the additive materials are preferably mobile enough within the extra-cellular spaces of the hollow fibers to be released therefrom upon demand. For example, the additive material can preferably be released from the hollow fibers upon application of a vacuum force or drawing action as mentioned above.
-
Hollow fibers 10 can also be incorporated into a cigarette filter to provide a means for controlling a resistance to draw (RTD) in a cigarette. In a preferred embodiment, a cigarette filter would includehollow fibers 10 therein. By providing hollow fibers in a cigarette, a cigarette can be provided with as little or as much resistance to draw as desired. - Additionally,
hollow fibers 10 can be used to supplement or replace multi-section filter assemblies, which are often more difficult to manufacture thanhollow fibers 10. Thus,hollow fibers 10 in cigarette filters could be used to simplify the manufacturing process while still providing tailored levels of RTD. - 2. Potting Materials
- As mentioned above, first and second filtrate obstructing or smoke impermeable materials can be used to obstruct smoke flow through a smoking article as illustrated in
FIGS. 1 and 4 . These filtrate obstructing or smoke impermeable materials along with semi-permeable or permeable material used to hold the hollow fibers can be generally referred to as “potting material.” - As used herein, “potting material” is intended to include materials that can be used to hold hollow fibers in place, as well as materials that can direct feed, filtrate, and retentate flow in, around and through lumens of the hollow fibers. As such, the potting material can be made of any non-toxic, permeable, semi-permeable or impermeable material that can hold the hollow fibers in a fixed positional relationship with one another (i.e., in parallel to one another). Further discussion of hollow fiber membranes in potting material can be found in U.S. Pat. Nos. 3,228,887, 3,528,553 and 6,685,832, which are hereby incorporated herein in their entireties by reference.
- Preferably, the potting material is a polymer or a composite, wherein the material can be selected depending upon the degree of permeability desired. For potting material used to obstruct airflow through an end of a hollow fiber, a filtrate impermeable or semi-permeable potting material may be desired. For example, epoxy is a filtrate impermeable potting material. On the other hand, for potting material used to hold the fibers in place, wherein filtrate obstruction is not desired, a permeable potting material may be desired. For example, cellulose acetate is a permeable potting material.
- The potting material can be formed on any portion of the
hollow fibers 10. For example, the potting material can be formed on a portion or the entirety of the length, the circumference of the fibers, and/or on ends of the hollow fibers. However, if the potting material is chosen to obstruct airflow, the potting material is preferably formed on less than the entire surface of the hollow fibers, as to allow for at least some filtrate to pass throughwalls 18 of thehollow fibers 10. - Additionally, less than full coverage of the
walls 18 of thehollow fibers 10 can be desired to not completely enclose and possibly isolate the extra-cellular spaces and additive materials that can be contained therein. As such, coverage by the potting material on thehollow fibers 10 is preferably less than 90% of the wall surface of thehollow fibers 10, and even more preferably, less than 60% of the wall surface of the hollow fibers 10 (e.g., 100-90%, 90-80%, 80-70%, 70-60%, 60-50%, 50-40%, 40-30%, 30-20%, 20-10% or 10-0%). - The potting material can be formed on the hollow fibers in any manner that provides the airflow controlling properties desired by the embodiment. For example, methods of forming potting material on hollow fibers have been discussed in U.S. Pat. Nos. 6,702,561, 6,663,745, 6,623,637 and 5,480,553, which are incorporated herein in their entireties by reference.
- As mentioned above, the potting material can be made of any material that can obstruct smoke passage. As such, the potting material can be made of an impermeable, semi-permeable or permeable material. If the potting material is a semi-permeable or permeable material, then the potting material can be used as permeable barrier and can increase the resistance to airflow therethrough.
- Therefore, a smoking article can be provided with hollow fibers in a conformation such that the structure and orientation for the
hollow fibers 10 allows for at least some of the extra-cellular spaces ofhollow fibers 10 to be accessible to hollow fibers. Additionally, as provided herein, the smoke flow can still be at least partially directed through thelumens 15 and thewalls 18 of thehollow fibers 10, wherein additive materials in the extra-cellular spaces can interact with the airflow as it passes through thewalls 18 of thehollow fibers 10. - 3. Outer Layer
- The
hollow fibers 10 can also include an outer layer covering or encapsulating the hollow fibers 10 (with additive material therein, if desired). Preferably, the outer layer is a solid wall or film, wherein the solid wall or film can be used to temporarily seal or encapsulate the hollow fibers 10 (and anything encapsulated within the hollow fibers 10) away from the surrounding environment. - Preferably, the outer layer is applied around the outer surfaces of the
hollow fibers 10 such that additive materials added to thehollow fibers 10 can be sealed within thehollow fibers 10, and/or within their extra-cellular spaces. Further, the outer layer is preferably easily frangible and can be ruptured to allow additive materials to be released from thehollow fibers 10. - The outer layer can be any frangible material, such as a polymer, which is capable of both sealing the hollow fibers, as well as breaking, rupturing or perforating on demand. Preferably, the outer layer is made of sugar or pectin, which can also be provided to flavor filtrate, such as smoke filtrate, contacting the outer layer if desired. The outer layer is preferably used to immobilize additive materials within the
hollow fibers 10, and thus preferably reduces dissipation of the additive material until the outer layer is broken, ruptured or perforated. - Preferably, the outer layer is a frangible thin film. By providing a frangible thin film, a difference in fluid pressure on either side of the outer layer and the hollow fiber walls (i.e., drawing on a cigarette with hollow fibers and the outer layer therein) can be sufficient to cause the outer layer to break to release the additive materials therefrom.
- For example, in a cigarette, an outer layer can be designed to break when smoke is drawn through the walls of the hollow fibers, wherein the vacuum pressure of drawing the smoke can cause the outer layer to break. In other words, when a smoker can puff on a cigarette causing the outer layer to be broken by the smoke being drawn through the walls of the hollow fibers and additive materials can be released into the smoke as it passed through the walls of the hollow fibers.
- The outer layer can be formed by any method capable of applying a film that is sufficiently thin to allow vacuum pressure to rupture the film. Preferably, the outer layer is applied by spraying a film forming material onto the outer surfaces of hollow fibers and allowing for the film forming material to solidify into a film to provide an outer layer.
- 4. Smoking Articles
- In a preferred embodiment, the
hollow fibers 10 are used in smoking articles, along with sorbents, such as microporous materials, to filter or remove gas phase constituents from cigarette smoke. Sorbents (i.e., microporous sorbents) such as an activated carbon and/or a zeolite sorbent can be used. - While any suitable material can be used as a sorbent, a preferred embodiment includes activated carbon. However, sorbents can hinder a cigarette designer's ability to add materials, such as volatile flavor components like menthol, as the sorbents can adsorb and/or absorb migrating volatile compounds during the time between cigarette manufacture and its being smoked.
- Two problems occur when additive materials, such as volatile flavor components, are included in smoking articles with sorbents: first, the additive materials can migrate throughout the smoking article; and second, the additive materials can be adsorbed or absorbed by the sorbents. These problems have previously been addressed by using centrally located flavor elements in commonly assigned U.S. patent application Ser. No. 2003/0224918, as well as filters for a smoking article containing a flavored hollow fiber in U.S. Pat. No. 4,971,078, both of which are incorporated herein in their entirety by reference.
- When additive materials are sorbed by sorbents, not only can additive materials be lost, but also the additive materials can also occupy active sites in the sorbent. If the additive materials occupy active sites in the sorbent, the ability of the sorbent to remove targeted gases or constituents from smoke can be compromised. However,
hollow fibers 10 can be used to overcome this problem by containing and isolating the additive materials from the sorbent prior to smoking, and therefore avoiding interaction between the additive materials and the sorbent during storage. - In a cigarette filter, in addition to the
hollow fibers 10 and the sorbent, a molecular sieve material can also be present. Preferably, the molecular sieve material can be present in monolithic or particle form sized at about 0.1 mm to 1 mm, and more preferably 0.3 mm to about 0.9 mm (e.g., 0.3 mm to 0.4 mm, 0.4 mm to 0.5 mm, 0.5 mm to 0.6 mm, 0.7 mm to 0.8 mm or 0.8 mm to 0.9 mm) to facilitate processing into cigarette filters so as to achieve a desirable filter pressure drop or RTD (resistance to draw). - Various filter constructions known in the art can be used, in which hollow
fibers 10 can be incorporated. Exemplary filter structures that can be used include, but are not limited to, a mono filter, a dual filter, a triple filter, a single or multi cavity filter, a recessed filter, a free-flow filter, combinations thereof and the like. Filter elements are typically constructed from cellulose acetate tow or cellulose paper materials. - The length and pressure drop of the segments in a dual filter can be adjusted to provide optimal sorption, while maintaining acceptable draw resistance. Triple filters can include mouth and smoking material or tobacco side segments, and a middle segment comprising paper. Cavity filters include two spaced-apart filter plugs. The filters can also be ventilated and/or comprise additional sorbents (such as activated carbon), catalysts or other additives suitable for use in a cigarette filter.
- Additionally, in an exemplary embodiment, a
cigarette 100 with a bundle ofhollow fibers 10 in thefilter 130 can also include asorbent 60. For example, as illustrated inFIG. 7 , acigarette 100 can be provided with afilter 130 which includeshollow fibers 10 with an additive material, such as a flavorant, therein and a sorbent upstream 60 (away from the smoker and toward the tobacco portion 50). As sorbents are typically effective for adsorbing or absorbing material added, such as a flavorant, placing thesorbent 60 upstream from the flavorant in thehollow fibers 10 can reduce the level of absorption or adsorption of the flavorant by thesorbent 60. - Preferably, the
hollow fibers 10 can be located in a portion of thefilter 130 downstream from thesorbent 60 with a section offilter material 70, such as cellulose acetate, between the two, as illustrated inFIG. 7 . Preferably, thehollow fibers 10 and thesorbent 60, if provided, would be placed in cavities within a filter assembly 40. However, both thehollow fibers 10 and thesorbent 60, if provided, can be placed anywhere within afilter 130 of a smoking article. - While a preferred filter includes a sorbent and
hollow fibers 10, thehollow fibers 10 can also be used in smoking articles without a sorbent in the filter, as illustrated inFIGS. 1 and 4 . Regardless of the type of article in which thehollow fibers 10 is incorporated, thehollow fibers 10 can be used to provide effective containment and delivery of materials, such as volatile flavors or other smoking related chemicals. - 5. Additives
- Hollow fibers can desirably be used to encapsulate additives in a smoking article, as mentioned above, wherein additives can be encapsulated within extra-cellular spaces of the hollow fibers. By such encapsulation, additives can both be protected from loss and can be mixed with entrainment air as air passes through the walls of the hollow fibers.
- In order to immobilize or encapsulate additives within
hollow fibers 10,hollow fibers 10 are preferably soaked in additives. Soaking allows the additives to be absorbed intoextra-cellular spaces 35 ofhollow fibers 10, where the additives can remain due to capillary forces, thus preventing dissipation of the additives. - The
hollow fibers 10 can preferably be placed in a smoking article, more preferably a cigarette filter, where thehollow fibers 10 are aligned in a cigarette for airflow. For example, the long axes of thehollow fibers 10 can be aligned with the long axis of the cigarette for airflow purposes. Also, adownstream potting material 30 can be used to obstruct fluid flow through the downstream end of thehollow fibers 10. - Additionally, an outer layer can be formed on the
hollow fibers 10 in order to prevent dissipation and to further encapsulate additive materials in extra-cellular spaces of the hollow fibers, as mentioned above. - The additives can be flavors, which can be selected from any number of known artificial and natural materials, such as, for example, peppermint, spearmint, wintergreen, menthol, cinnamon, chocolate, coffee, tobacco, vanillin, licorice, clove, anise, sandalwood, geranium, rose oil, vanilla, lemon oil, cassia, spearmint, fennel, ginger, ethylacetate, isoamylacetate, propylisobutyrate, isobutylbutyrate, ethylbutyrate, ethylvalerate, benzylformate, limonene, cymene, pinene, linalool, geraniol, citronellol, citral, peppermint oil, orange oil, coriander oil, borneol, fruit extract and the like. Illustrative of such tobacco flavorants are those described in U.S. Pat. Nos. 3,580,259; 3,625,224; 3,722,516; 3,750,674; 3,879,425; 3,881,025; 3,884,247; 3,890,981; 3,903,900; 3,914,451; 3,915,175; 3,920,027; 3,924,644; 3,966,989; 4,318,417; and the like, which are incorporated herein by reference in their entirety.
- The additives can also be chemicals, wherein the chemicals can be used to attract or repel aerosols, or react with smoke constituents to remove or chemically extract smoke constituents.
- For example, chemicals which can be used to attract or repel aerosols include surfactants containing distinct hydrophobic (apolar) and hydrophilic (polar) regions. For example, polar surfactants can be used to attract or repel selected tobacco smoke constituents like polar tobacco constituents due to intrinsic attractive polarity properties. For example, by attracting tobacco smoke constituents, these tobacco smoke constituents can be trapped and held within the hollow fibers chemically (in addition to mechanically being selectively separated by pore size of the walls of the hollow fibers, as mentioned above).
- As mentioned above, chemicals or chemical systems can also be used to react with smoke constituents to remove smoke constituents. For example, chemical systems such as aminopropylsilyl (APS), aminoethyl aminopropylsilyl (AEAPS) and aminoethylaminoethyl aminopropylsilyl (AEAEAPS) can be used. See commonly assigned U.S. Pat. Nos. 6,595,218 and 6,209,547, both of which are hereby incorporated herein by reference in their entirety.
- As mentioned above, chemicals can also be used to react with smoke constituents to extract smoke constituents. The term “chemical extractive smoking” is intended to mean providing predetermined tobacco smoke constituents to a smoker without any combustion of tobacco (i.e., smokeless smoking).
- Chemical extractive smoking provides a chemical or reagent, such as water or alcohol, for interaction with tobacco in a tobacco product. By allowing the chemical or reagent to interact with tobacco, a tobacco enriched chemical or reagent can be formed, which in turn can be inhaled as a vapor or aerosol. For example, the chemical or reagent can be solvents, such as water or alcohol, such as ethyl alcohol. Preferably, the chemical extractive smoking occurs at lower than combustion temperatures; however heat can be utilized to promote vaporization (or volatilization) of the tobacco enriched chemical or reagent.
- However, it is noted that heat can be used to increase the vapor and the solubility of the tobacco constituents for “smoking.” By using heat, the tobacco enriched chemical or reagent can be heat vaporized and the mobilization of the tobacco properties within the vapor can potentially be increased.
- As an exemplary embodiment of a chemical extractive smoking article, a cigarette can be made with hollow fibers including immobilized chemicals therein. When “smoked,” the drawing action on one side of the
hollow fibers 10 releases chemicals into the tobacco, whereupon the chemicals cause extractive release of a tobacco aerosol. - While the invention has been described in detail with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made, and equivalents employed, without departing from the scope of the appended claims.
Claims (34)
1. A cigarette, comprising:
a tobacco rod;
a filter operative with the tobacco rod, wherein the filter comprises a bundle of hollow fibers, wherein the lumens of the hollow fibers are aligned axially in parallel to one another; and
an additive material in extra-cellular spaces of the hollow fibers,
wherein one end of at least one of the hollow fibers is obstructed.
2. The cigarette of claim 1 , wherein the filter further comprises a plug of fibrous filter material, wherein the plug is located upstream and/or downstream from the hollow fibers in the filter.
3. The cigarette of claim 1 , wherein the hollow fibers are located in a cavity of the filter.
4. The cigarette of claim 1 , wherein the obstructed end of the at least one of the hollow fibers comprises a first smoke impermeable material located within the lumen of the at least one of the hollow fibers, wherein the impermeable material obstructs airflow through the obstructed end of the at least one of the hollow fibers.
5. The cigarette of claim 4 , wherein the first smoke impermeable material comprises a polymer or a composite.
6. The cigarette of claim 1 , further comprising a second smoke impermeable material surrounding an upstream or a downstream end of the bundle of hollow fibers, wherein the second smoke impermeable material obstructs airflow around the bundle of hollow fibers and directs airflow into lumens of the bundle of hollow fibers.
7. The cigarette of claim 6 , wherein the first smoke impermeable material comprises a polymer or a composite.
8. The cigarette of claim 1 , further comprising an outer layer on the hollow fibers, wherein the outer layer and the hollow fibers comprise different materials.
9. The cigarette of claim 8 , wherein the outer layer comprises sugar or pectin.
10. The cigarette of claim 1 , wherein the hollow fibers comprise a polymeric material.
11. The cigarette of claim 1 , wherein the hollow fibers comprise cellulose, modified cellulose, cellulose acetate, polypropylene, polysulfone, acrylic compounds, silicone rubber, or mixtures or combinations thereof.
12. The cigarette of claim 1 , wherein the additive material comprises a flavorant, a reagent which chemically reacts with and selectively separates a gaseous component of a smoke stream, a surfactant, a solvent, or mixtures or combinations thereof.
13. The cigarette of claim 12 , wherein the additive material comprises menthol.
14. The cigarette of claim 1 , wherein the hollow fibers comprise a bundle of fibers, and wherein the cigarette further comprises a ring, wherein the ring surrounds the bundle of fibers.
15. The cigarette of claim 1 , wherein the hollow fibers comprises a bundle of fibers, and wherein the cigarette further comprises an adhesive, wherein the adhesive bonds walls of the bundle of fibers to other walls of the bundle of fibers.
16. The cigarette of claim 1 , wherein each of the hollow fibers has a lumen diameter of approximately 50 microns to approximately 1500 microns.
17. The cigarette of claim 1 , wherein each of the hollow fibers has a lumen an inner diameter of approximately 90 microns to approximately 450 microns.
18. The cigarette of claim 1 , wherein the filter further comprises a sorbent.
19. The cigarette of claim 18 , wherein the sorbent is located upstream in the filter from the hollow fibers.
20. The cigarette of claim 1 , wherein the lumens of the hollow fibers are aligned with one another in a direction in which smoke will travel through the cigarette.
21. A cigarette filter, comprising:
hollow fibers;
an outer layer covering an outer region of the hollow fibers; and
cellulose acetate, wherein the hollow fibers and the outer layer are embedded within the cellulose acetate.
22. The cigarette filter of claim 21 , further comprising an additive material in extra-cellular spaces in the hollow fibers.
23. The cigarette filter of claim 22 , wherein the additive material comprises a flavorant, a reagent which chemically reacts with and selectively separates a gaseous component of a smoke stream, a surfactant, a solvent, or mixtures or combinations thereof.
24. The cigarette filter of claim 22 , further comprising a first smoke impermeable material located between outer surfaces of the hollow fibers and the inner diameter of the cigarette filter on one end of at least one of the hollow fibers, and a second smoke impermeable material located on end portions of lumens of the hollow fibers at the other end of the hollow fibers.
25. The cigarette filter of claim 22 , wherein the outer layer comprises sugar or pectin.
26. A method of manufacturing a cigarette filter, comprising:
preparing hollow fibers with a smoke impermeable material covering one end of at least one of the hollow fibers;
at least partially filling extra-cellular spaces within the hollow fibers with an additive material; and
placing the hollow fibers with the smoke impermeable material and the additive material in a cigarette filter.
27. The method of claim 26 , wherein the at least partially filling the extra-cellular spaces within the hollow fibers with the additive material comprises soaking the hollow fibers in the additive material for a time effective to at least partially fill the extra-cellular spaces with the additive material.
28. The method of claim 26 , further comprising forming an outer layer on an outer surface of the hollow fibers before placing the hollow fibers in the cigarette filter.
29. The method of claim 28 , wherein the forming of the outer layer comprises spraying a layer of pectin or sugar on the outer surface of the hollow fibers.
30. A method of treating mainstream smoke, comprising:
drawing tobacco smoke axially through hollow fibers, wherein the mainstream tobacco smoke is drawn into an open upstream end into lumens of the hollow fibers and is drawn through permeable walls of the hollow fibers to a downstream end of a smoking article.
31. A cigarette filter comprising a hollow fiber membrane, wherein the hollow fiber membrane comprises:
hollow fibers; and
a smoke impermeable material, wherein the smoke impermeable material obstructs a downstream end of a lumen of the hollow fiber.
32. The cigarette filter of claim 31 , wherein the hollow fiber membrane comprises more than one hollow fiber bundled and aligned in a direction parallel to one another and parallel to an axial direction of the cigarette filter, and/or wherein the hollow fiber comprises a porous, permeable material.
33. The cigarette filter of claim 31 , further comprising an additive material in extra-cellular spaces of the hollow fibers.
34. The cigarette filter of claim 33 , wherein the additive material comprises a flavorant, a reagent which chemically reacts with and selectively separates a gaseous component of a smoke stream, a surfactant, a solvent, or mixtures thereof.
Priority Applications (22)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/241,978 US20070074733A1 (en) | 2005-10-04 | 2005-10-04 | Cigarettes having hollow fibers |
EA200801010A EA013252B1 (en) | 2005-10-04 | 2006-10-04 | Cigarettes having hollow fibers |
AU2006313451A AU2006313451B2 (en) | 2005-10-04 | 2006-10-04 | Cigarettes having hollow fibers |
CN2006800366469A CN101277621B (en) | 2005-10-04 | 2006-10-04 | Cigarettes having hollow fibers |
DE602006013007T DE602006013007D1 (en) | 2005-10-04 | 2006-10-04 | CIGARETTES WITH HOLLOW FIBERS |
DK06842326.8T DK1933654T3 (en) | 2005-10-04 | 2006-10-04 | Hollow fiber cigarettes |
SI200630621T SI1933654T1 (en) | 2005-10-04 | 2006-10-04 | Cigarettes having hollow fibers |
KR1020087009630A KR101322961B1 (en) | 2005-10-04 | 2006-10-04 | Cigarettes having hollow fibers |
PCT/IB2006/003884 WO2007054826A2 (en) | 2005-10-04 | 2006-10-04 | Cigarettes having hollow fibers |
AT06842326T ATE460852T1 (en) | 2005-10-04 | 2006-10-04 | HOLLOW FIBER CIGARETTES |
UAA200804554A UA91561C2 (en) | 2005-10-04 | 2006-10-04 | Cigarettes including hollow fibers |
MYPI20080821A MY143613A (en) | 2005-10-04 | 2006-10-04 | Cigarettes having hollow fibers |
CA2623219A CA2623219C (en) | 2005-10-04 | 2006-10-04 | Cigarettes having hollow fibers |
ES06842326T ES2340528T3 (en) | 2005-10-04 | 2006-10-04 | CIGARETTES WITH HOLLOW FIBERS. |
JP2008534108A JP5188395B2 (en) | 2005-10-04 | 2006-10-04 | Cigarette with hollow fiber |
EP06842326A EP1933654B1 (en) | 2005-10-04 | 2006-10-04 | Cigarettes having hollow fibers |
PL06842326T PL1933654T3 (en) | 2005-10-04 | 2006-10-04 | Cigarettes having hollow fibers |
BRPI0616851-5A BRPI0616851A2 (en) | 2005-10-04 | 2006-10-04 | cigarettes, method of manufacturing a cigarette filter and cigarette filter |
PT06842326T PT1933654E (en) | 2005-10-04 | 2006-10-04 | Cigarettes having hollow fibers |
IL190296A IL190296A (en) | 2005-10-04 | 2008-03-19 | Cigarettes comprising filters having hollow fibers |
ZA200802584A ZA200802584B (en) | 2005-10-04 | 2008-03-20 | Cigarettes having hollow fibers |
HK08110429.2A HK1115007A1 (en) | 2005-10-04 | 2008-09-19 | Cigarettes having hollow fibers |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/241,978 US20070074733A1 (en) | 2005-10-04 | 2005-10-04 | Cigarettes having hollow fibers |
Publications (1)
Publication Number | Publication Date |
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US20070074733A1 true US20070074733A1 (en) | 2007-04-05 |
Family
ID=37900741
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US11/241,978 Abandoned US20070074733A1 (en) | 2005-10-04 | 2005-10-04 | Cigarettes having hollow fibers |
Country Status (22)
Country | Link |
---|---|
US (1) | US20070074733A1 (en) |
EP (1) | EP1933654B1 (en) |
JP (1) | JP5188395B2 (en) |
KR (1) | KR101322961B1 (en) |
CN (1) | CN101277621B (en) |
AT (1) | ATE460852T1 (en) |
AU (1) | AU2006313451B2 (en) |
BR (1) | BRPI0616851A2 (en) |
CA (1) | CA2623219C (en) |
DE (1) | DE602006013007D1 (en) |
DK (1) | DK1933654T3 (en) |
EA (1) | EA013252B1 (en) |
ES (1) | ES2340528T3 (en) |
HK (1) | HK1115007A1 (en) |
IL (1) | IL190296A (en) |
MY (1) | MY143613A (en) |
PL (1) | PL1933654T3 (en) |
PT (1) | PT1933654E (en) |
SI (1) | SI1933654T1 (en) |
UA (1) | UA91561C2 (en) |
WO (1) | WO2007054826A2 (en) |
ZA (1) | ZA200802584B (en) |
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-
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- 2006-10-04 DE DE602006013007T patent/DE602006013007D1/en active Active
- 2006-10-04 EA EA200801010A patent/EA013252B1/en not_active IP Right Cessation
- 2006-10-04 BR BRPI0616851-5A patent/BRPI0616851A2/en not_active IP Right Cessation
- 2006-10-04 AT AT06842326T patent/ATE460852T1/en active
- 2006-10-04 JP JP2008534108A patent/JP5188395B2/en not_active Expired - Fee Related
- 2006-10-04 DK DK06842326.8T patent/DK1933654T3/en active
- 2006-10-04 PT PT06842326T patent/PT1933654E/en unknown
- 2006-10-04 CA CA2623219A patent/CA2623219C/en not_active Expired - Fee Related
- 2006-10-04 UA UAA200804554A patent/UA91561C2/en unknown
- 2006-10-04 SI SI200630621T patent/SI1933654T1/en unknown
- 2006-10-04 KR KR1020087009630A patent/KR101322961B1/en not_active IP Right Cessation
- 2006-10-04 EP EP06842326A patent/EP1933654B1/en not_active Not-in-force
- 2006-10-04 WO PCT/IB2006/003884 patent/WO2007054826A2/en active Application Filing
- 2006-10-04 AU AU2006313451A patent/AU2006313451B2/en not_active Ceased
- 2006-10-04 MY MYPI20080821A patent/MY143613A/en unknown
- 2006-10-04 PL PL06842326T patent/PL1933654T3/en unknown
- 2006-10-04 CN CN2006800366469A patent/CN101277621B/en not_active Expired - Fee Related
- 2006-10-04 ES ES06842326T patent/ES2340528T3/en active Active
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2008
- 2008-03-19 IL IL190296A patent/IL190296A/en not_active IP Right Cessation
- 2008-03-20 ZA ZA200802584A patent/ZA200802584B/en unknown
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US20090007925A1 (en) * | 2007-06-21 | 2009-01-08 | Philip Morris Usa Inc. | Smoking article filter having liquid additive containing tubes therein |
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US11129405B2 (en) | 2010-03-26 | 2021-09-28 | Philip Morris Usa Inc. | Inhibition of sensory irritation during consumption of non-smokeable tobacco products |
US11388923B2 (en) | 2010-03-26 | 2022-07-19 | Philip Morris Usa Inc. | Inhibition of undesired sensory effects by the compound camphor |
US8952038B2 (en) | 2010-03-26 | 2015-02-10 | Philip Morris Usa Inc. | Inhibition of undesired sensory effects by the compound camphor |
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US10117453B2 (en) | 2010-03-26 | 2018-11-06 | Philip Morris Usa Inc. | Inhibition of sensory irritation during consumption of non-smokeable tobacco products |
US10201180B2 (en) | 2010-03-26 | 2019-02-12 | Philips Morris Usa Inc. | Inhibition of undesired sensory effects by the compound camphor |
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US10952464B2 (en) | 2010-11-26 | 2021-03-23 | Filtrona Filter Products Development Co. Pte. Ltd. | Tobacco smoke filter |
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US11812780B2 (en) | 2010-11-26 | 2023-11-14 | Filtrona Filter Products Development Co. Pte. Ltd. | Tobacco smoke filter |
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Also Published As
Publication number | Publication date |
---|---|
EA200801010A1 (en) | 2008-08-29 |
ZA200802584B (en) | 2009-03-25 |
ATE460852T1 (en) | 2010-04-15 |
UA91561C2 (en) | 2010-08-10 |
CA2623219C (en) | 2014-08-19 |
WO2007054826A3 (en) | 2007-11-22 |
KR101322961B1 (en) | 2013-10-29 |
HK1115007A1 (en) | 2008-11-14 |
EP1933654B1 (en) | 2010-03-17 |
JP2009509563A (en) | 2009-03-12 |
AU2006313451A1 (en) | 2007-05-18 |
CA2623219A1 (en) | 2007-05-18 |
IL190296A (en) | 2012-06-28 |
BRPI0616851A2 (en) | 2011-07-05 |
AU2006313451B2 (en) | 2011-04-21 |
SI1933654T1 (en) | 2010-05-31 |
DK1933654T3 (en) | 2010-07-12 |
KR20080059582A (en) | 2008-06-30 |
CN101277621B (en) | 2011-04-13 |
EP1933654A2 (en) | 2008-06-25 |
WO2007054826A2 (en) | 2007-05-18 |
DE602006013007D1 (en) | 2010-04-29 |
JP5188395B2 (en) | 2013-04-24 |
ES2340528T3 (en) | 2010-06-04 |
EA013252B1 (en) | 2010-04-30 |
IL190296A0 (en) | 2009-09-22 |
PT1933654E (en) | 2010-04-26 |
MY143613A (en) | 2011-06-15 |
PL1933654T3 (en) | 2010-07-30 |
CN101277621A (en) | 2008-10-01 |
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